Catalysts for halogenated hydrocarbon processing, their precursors and their preparation and use

ABSTRACT

Processes are disclosed for decreasing the chlorine to carbon ratio for halogenated hydrocarbons containing chlorine and from 1 to 6 carbon atoms, in the presence of a multiphase catalyst. The processes each involve (1) preparing a single phase solid catalyst precursor which has a structure that collapses at a temperature of about 400° C. or less and has the formula (NH 3 ) 6  Ru l-r-s  Co r  Cr s  MF 6 , where r+s is in the range of 0.00 to 0.99, and M is at least one trivalent metal selected from the group consisting of Al, Cr, Fe, V, Sc and Ga; and (2) producing the multiphase catalyst by heating the single phase solid catalyst precursor to about 400° C. or less in an non-oxidizing atomsphere to produce a multiphase composition wherein a phase containing ruthenium is homogeneously dispersed with a phase containing metal fluoride. 
     Also disclosed are single phase fluoride compositions having the formula (NH 3 ) 6  Ru l-r-s  Co r  Cr s  MF 6 , where r+s is in the range of 0.00 to 0.99, and M is at least one trivalent element selected from the group consisting of Al, Cr, Fe, V, Sc and Ga; and multiphase catalyst compositions consisting essentially of metallic ruthenium and fluorides of at least one element selected from the group consisting of Al, Co, Cr, Fe, V, Sc and Ga, wherein the ruthenium is homogeneously dispersed with phases of the fluorides.

This application represents a national filing under 35 USC 371 of International Application No. PCT/US96/18967 filed Nov. 26, 1996, and claims priority of U.S. Provisional Application No. 60/007,734 filed Nov. 29, 1995.

FIELD OF THE INVENTION

This invention relates to fluoride compositions and their preparation and use, and more particularly to ruthenium and selected metal fluoride catalysts, precursors for such catalysts, and preparation and use of such catalysts for processing halogenated hydrocarbons.

BACKGROUND

A variety of metal catalysts have been proposed for use in processes for dimerizing chlorine-containing fluorocarbons, for dehalogenating halogenated fluorocarbons, for hydrofluorinating halogenated hydrocarbons and for hydrodehalogenating halogenated fluorocarbons (see e.g., PCT Publication No. WO 95/05353 for dimerization examples and L. E. Manzer et al., Adv. Catal. (39) pp. 329-350 (1993) for examples of the other listed processes). The catalysts proposed include catalysts involving combinations of cations. Typically these materials are prepared by depositing a soluble salt of the metal on a support, e.g., silica, alumina and carbon. While this method does provide a combination catalyst, the support material and the material deposited thereon are not uniformly dispersed. Techniques such as coprecipitation which rely upon physical characteristics of individual components (e.g., solubility) also typically yield non-homogeneously dispersed products due to differences in physical and chemical properties of the components. There is an interest in developing means for more homogeneous dispersion of components of multiple cation catalysts which can be used for dimerizing, dehalogenating, hydrofluorinating and hydrodehalogenating halogenated hydrocarbons.

SUMMARY OF THE INVENTION

This invention provides processes for decreasing the chlorine to carbon ratio for halogenated hydrocarbons containing chlorine and from 1 to 6 carbon atoms, in the presence of a multiphase catalyst. The processes are each characterized by (1) preparing a single phase solid catalyst precursor which has a structure that collapses at a temperature of about 400° C. or less and has the formula (NH₃)₆ Ru_(l-r-s) Co_(r) Cr_(s) MF₆, where r+s is in the range of 0.00 to 0.99, and M is at least one trivalent metal selected from the group consisting of Al, Cr, Fe, V, Sc and Ga; and (2) producing said multiphase catalyst by heating said single phase solid catalyst precursor to about 400° C. or less in a non-oxidizing atmosphere to produce a multiphase composition wherein a phase containing ruthenium is homogeneously dispersed with a phase containing metal fluoride.

This invention further provides single phase fluoride compositions of the formula (NH₃)₆ Ru_(1-r-s) Co_(r) Cr_(s) MF₆, where r+s is in the range of 0.00 to 0.99, and M is at least one trivalent element selected from the group consisting of Al, Cr, Fe, V, Sc and Ga. This invention also provides multiphase catalyst compositions consisting essentially of metallic ruthenium and fluorides of at least one element selected from the group consisting of Al, Co, Cr, Fe, V, Sc and Ga, wherein said ruthenium is homogeneously dispersed with phases of said fluorides.

DETAILED DESCRIPTION

The catalytic processes of this invention include processes for dimerizing, processes for dehalogenating, processes for hydrofluorinating and processes for hydrodehalogenating chlorinated fluorocarbons (i.e., compounds containing only carbon, chlorine and fluorine) and chlorinated hydrofluorocarbons (i.e., compounds containing only carbon, hydrogen, chlorine and fluorine). The chlorinated fluorocarbons and chlorinated hydrofluorocarbons can contain from 1 to 6 carbon atoms. The processes employ a multiphase catalyst prepared in a manner which provides a homogeneous dispersion of ruthenium metal. In accordance with this invention, the catalyst may be made by preparing a decomposable single phase solid catalyst precursor and then converting the precursor to a multiple phase catalyst containing fluorine. In this multiple phase catalyst all the metals other than ruthenium consist essentially of the metal fluorides. A single phase catalyst precursor of the formula (NH₃)₆ Ru_(l-r-s) Co_(r) Cr_(s) F₆ may be prepared from aqueous solutions of hexaamine ruthenium trichloride (NH₃)₆ RuCl₃, (NH₃)₆ CoCl₃, (NH₃)₆ CrCl₃, and trivalent metal chlorides, MCl₃, selected from the group of consisting of AlCl₃, CoCl₃, CrCl₃, FeCl₃, VCl₃, GaCl₃ and ScCl₃, taken in the stoichiometric ratios, Ru:Co:Cr:M=(l-r-s):r:s:l, where r+s is in the range of 0.00 to 0.99 (preferably from 0.10 to 0.90, and more preferably from 0.20 to 0.80) by direct precipitation using aqueous HF (e.g., 48% HF) as the precipitant. The single phase catalyst precursor can also be prepared by dissolving the metal oxides, M₂ O₃ (i.e., Al₂ O₃, Co₂ O₃, Cr₂ O₃, Fe₂ O₃, V₂ O₃, Ga₂ O₃ or SC₂ O₃) in aqueous HF (e.g., 48% HF), combining the metal solutions with (NH₃)₆ RuCl₃, (NH₃)₆ CoCl₃ or (NH₃)₆ CrCl₃ taken in the stoichiometric ratios, Ru:Co:Cr:M=(l-r-s):r:s: 1, and employing direct precipitation using the aqueous HF as a precipitant. The recovered solid can be dried at about 110° C. for about 12 hours. Powder X-ray diffraction patterns of catalyst precursors show the formation of single phase products and can be indexed on the basis of a cubic unit cell (space group: Pa3). Infrared and Raman spectra of the catalyst precursors show the presence of hexaammine groups. The microprobe analysis of the catalyst precursors show the Ru:Co:Cr:M:F ratio to be (l-r-s):r:s:1:6. As noted above r+s is in the range of 0.00 to 0.99. Included are embodiments where r is 0.00 and s is up to 0.99, and embodiments where s is 0.00 and r is up to 0.99. Of note for high chromium content are embodiments where r is 0.00 and M is Cr.

It will be evident that providing single phase catalyst precursors as described arranges the components in a structured arrangement where Ru and the other metal components are closely connected through the NH₃ and/or F components. In any case, as a result of the arrangement of the components in the precursor, when the single phase structure collapses upon heating, uniformly interspersed phases of ruthenium and metal fluorides are formed. These are referred to herein as "homogeneously dispersed" phases.

It is desirable to convert the single phase precursor to a homogeneously dispersed multiphase composition at a moderately elevated temperature of about 400° C. or less, preferably about 300° C. to 400° C. Conversion to the homogeneously dispersed multiphase composition is conducted in a non-oxidizing atmosphere. By non-oxidizing atmosphere is meant an atmosphere where the ruthenium metal formed by decomposition of the precursor is not oxidized. This multiphase composition can be used as a catalyst for dimerizing, dehalogenating, hydrofluorinating and hydrodehalogenating halogenated hydrocarbons containing chlorine and from 1 to 6 carbon atoms. Preferred uses include use as a catalyst for dimerizing and dehalogenating.

Included in this invention is a process for dimerizing saturated compounds having the formula C_(n) H_(a) Cl_(b) F_(c) where n is an integer from 1 to 4, a is an integer from 0 to 1, b is an integer from 2 to 9, c is an integer from 0 to 9, where a+b+c equals 2n+2, and where two chlorines that are removed are on the same carbon atom, by reacting said compound with hydrogen in the vapor phase to produce olefins of the formula C_(2n) H_(2a) Cl_(2b-4) F_(2c) ; a process for dehalogenating a saturated compound having the formula C_(m) H_(d) Cl_(e) F_(f) where m is an integer from 2 to 6, d is an integer from 0 to 2, e is an integer from 2 to 4, f is an integer from 3 to 12, where d+e+f equals 2m+2, by reacting said compound with hydrogen in the vapor phase to produce olefins of the formula C_(m) H_(d) Cl_(e-y) F_(f-y), where y is an integer from 1 to 2 when m is an integer from 2 to 3, and y is an integer from 2 to 4 when m is an integer from 4 to 6, provided that a chlorine atom on each of two adjacent carbons or a fluorine and a chlorine atom on two adjacent carbons, but not a fluorine atom on each of two adjacent carbons are removed; a process for increasing the fluorine content of a saturated or olefinic compound having the formula C_(j) H_(g) Cl_(h) F_(i) where j is an integer from 1 to 6, g is an integer from 0 to 4, h is an integer from 1 to 13, i is an integer from 0 to 13, provided that h is at least 1 when the compound is saturated, by reacting said compound with HF in the vapor phase; and a process for the hydrodechlorination of suitable cyclic and acyclic compounds having the formula C_(k) H_(p) Cl_(q) F_(t) where k is an integer from 1 to 6, p is an integer from 0 to 12, q and t are integers from 1 to 13, where p+q+t equals 2k+2, when the compound is saturated and acyclic, equals 2k when the compound is saturated and cyclic or is olefinic and acyclic, and equals 2k-2 when the compound is olefinic and cyclic, by reacting said compound with hydrogen in the vapor phase.

Homogeneously dispersed multiphase catalysts of ruthenium and fluorides of at least one element selected from the group consisting of Al, Co, Cr, Fe, V, Sc and Ga may be used in accordance with this invention in a process for dimerizing saturated compounds having the formula C_(n) H_(a) Cl_(b) F_(c), by contacting the saturated compounds with the homogeneously dispersed multiphase catalysts in the presence of hydrogen in the vapor phase. Suitable catalysts for this reaction include compositions consisting essentially of fluorides of at least one element selected from the above disclosed group homogeneously dispersed with ruthenium.

The reaction of said compounds of the formula C_(n) H_(a) Cl_(b) F_(c) with hydrogen is conducted in the presence of the catalysts of the instant invention. Typically the reaction is conducted at a temperature from about 100° C. to 400° C., preferably from about 125° C. to 375° C. and more preferably from about 150° C. to about 300° C. Typically, the contact time is from about 1 to about 100 seconds, preferably from about 5 to about 60 seconds. The mole ratio of hydrogen to C_(n) H_(a) Cl_(b) F_(c) compound(s) ordinarily should be at least about 0.25:1. Typically, the molar ratio of hydrogen to said compounds of the formula C_(n) H_(a) Cl_(b) F_(c) ranges from about 0.5:1 to about 10:1, and is preferably from about 0.5:1 to 5:1, and more preferably from about 0.5:1 to 2:1. In general, with a given catalyst composition, the higher the temperature and the longer the contact time, the greater is the conversion to dimerized products. The above variables can be balanced, one against the other, so that the formation of dimerized products is maximized.

Examples of halogenated hydrocarbons of the formula C_(n) H_(a) Cl_(b) F_(c) which may be reacted with hydrogen include, CCl₄, CCl₃ CClF₂, CCl₃ CF₃, CF₃ CCl₂ CF₃, CCl₃ CF₂ CF₃, CCl₃ CF₂ CF₂ CF₃ and CF₃ CCl₂ CF₂ CF₃. Of note is a catalytic process for producing cis and trans 2,3-dichloro-1,1,1,4,4,4-hexafluorobutene-2 (i.e., F1316mxx or CF₃ CCl═CClCF₃) by the reaction of hydrogen with CCl₃ CF₃. This dimerization reaction is done in the presence of the catalysts of the instant invention and is preferably conducted at a temperature of from about 125° C. to 300° C., more preferably from about 150° C. to 250° C.

Also of note is a catalytic process for producing cis and trans 3,4dichloro-1,1,1,2,2,5,5,6,6,6-decafluorohexene-3 (i.e., F151-10mcxx or C₂ F₅ CCl═CClC₂ F₅). Starting materials include 1,1,1-trichloro-2,2,3,3,3-pentafluoropropane. A catalytic process for producing 2,3-trifluoromethyl-1,1,1,4,4,4-hexafluorbutene-2 (i.e., F151-12mmtt or (CF₃)₂ C═C(CF₃)₂ from 2,2-dichloro-1,1,1,3,3,3-hexafluoropropane is also of note.

The dimerized products which are unsaturated and/or contain chlorine can be further reacted with hydrogen or a fluorinating agent (e.g., HF) in the presence of the same or optionally a second catalyst. Further reacting the dimerized products with hydrogen (optionally using a second catalyst) can produce hydrofluorocarbons. Reaction with a fluorinating agent can produce a hydrofluorocarbon or a perfluorinated alkane, depending on the fluorinating agent.

The catalyst used for the hydrogenation reaction may be the same catalyst used for the dimerization reaction or may be selected from metals known to provide significant hydrogenolysis activity on supports such as alumina, fluorided alumina and carbon. A preferred catalyst contains at least one metal selected from the group consisting of rhenium, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum supported on carbon with an ash content of less than 0.5% by weight. The reaction of the dimerized products and hydrogen can be performed in liquid or vapor-phase using well-known chemical engineering practice, which includes continuous, semi-continuous or batch operations. The hydrogenolysis process is achieved at atmospheric or superatmospheric pressures.

The fluorinating agent may be chosen from the group consisting of hydrogen fluoride, cobalt fluoride, elemental fluorine or fluoride salts. Any of the known art catalysts and conditions may be used for the hydrofluorination in either the vapor phase (e.g., chromium oxide) or the liquid phase (e.g., an antimony halide).

Homogeneously dispersed multiphase catalysts of ruthenium and fluorides of at least one element selected from the group consisting of Al, Co, Cr, Fe, V, Sc and Ga may be used in accordance with this invention in a process for dehalogenating saturated compounds having the formula C_(m) H_(d) Cl_(e) F_(f), by contacting the saturated compounds with the homogeneously dispersed multiphase catalysts in the presence of hydrogen in the vapor phase. Suitable catalysts for this reaction include compositions consisting essentially of fluorides of at least one element selected from the above disclosed group homogeneously dispersed with ruthenium.

The reaction of said compounds of the formula C_(m) H_(d) Cl_(c) F_(f) with hydrogen is conducted in the presence of the catalysts of the instant invention. Typically the reaction is conducted at a temperature from about 100° C. to 350° C., preferably from about 125° C. to 325° C., and more preferably from about 150° C. to about 275° C. Typically the contact time is from about 1 to about 100 seconds, preferably from about 5 to about 60 seconds. The molar ratio of hydrogen to C_(m) H_(d) Cl_(c) F_(f) compound(s) ordinarily should be at least about 1:1. Typically, the molar ratio of hydrogen to said compounds of the formula C_(m) H_(d) Cl_(e) F_(f) ranges from about 1:1 to about 5:1, preferably from about 1:1 to 3:1, and more preferably from about 1:1 to 2:1. In general, with a given catalyst composition, the higher the temperature and the longer the contact time, the greater is the conversion to dehalogenated products. The above variables can be balanced, one against the other, so that the formation of dehalogenated products is maximized.

Examples of halogenated hydrocarbons of the formula C_(m) H_(d) Cl_(c) F_(f) which may be reacted with hydrogen include CCl₂ FCClF₂, CClF₂ CCl₂ CF₃, CClF₂ CClFCClF₂, CClF₂ CF₂ CClF₂, CClF₂ CClFCF₃ and CCl₂ FCF₂ CF₃. Of note is a catalytic process for producing 1,1,3,3,3-pentafluoropropene-1 (i.e., F1225zc or CF₂ ═CHCF₃) by the reaction of hydrogen with CClF₂ CHClCF₃. This dehalogenation reaction is done in the presence of the catalysts of the instant invention and is preferably conducted at about 125° C. to 325° C., more preferably about 150° C. to 275° C.

Also of note is a catalytic process for producing hexafluoropropene (i.e., HFP or CF₂ ═CFCF₃). The starting material is 1,2-dichloro-1,1,2,3,3,3-hexafluoropropane. A catalytic process for producing 1-chloro-1,2,2-trifluoroethene (i.e., CTFE or CClF═CF₂) from 1,1,2-trichloro-1,2,2-trifluoroethane is also of note.

In another embodiment of this invention isomer mixtures can be reacted using the catalysts of this invention to afford products resulting from dimerization of one isomer and dehalogenation of the other isomer. For example, a mixture of CCl₃ CF₃ and CCl₂ FCClF₂ (i.e., C₂ Cl₃ F₃ isomers) can be reacted with hydrogen in the presence of the catalysts of the instant invention at from about 100° C. to 300° C., preferably at from about 125° C. to 275° C., and more preferably at from about 150° C. to about 250° C., with a contact time of from about 1 to about 100 seconds, preferably from about 5 to about 60 seconds. The ratio of hydrogen to the C₂ Cl₃ F₃ isomers ordinarily should be at least about 0.5:1. Typically, the molar ratio of hydrogen to the C₂ Cl₃ F₃ isomers is within the range of from about 0.5:1 to about 10:1, preferably from about 0.5:1 to 5:1, and more preferably from about 0.5:1 to 2:1. The product of the reaction contains CF₃ CCl═CClCF₃ from CCl₃ CF₃ dimerization and CClF═CF₂ from CCl₂ FCClF₂ dehalogenation. If a mixture of C₂ Cl₃ F₃ isomers which contains less than about 10% of the CCl₃ CF₃ (CFC-113a) isomer is reacted in the same manner at temperatures at or below about 150° C., then CFC-113a is predominantly dimerized to CF₃ CCl=CClCF₃ and small amounts of other hydrogenated products. Very little of the CCl₂ FCClF₂ (CFC-1 13) isomer is dehalogenated to CTFE. This procedure can be used to obtain pure CFC-113. In the same manner a mixture of CCl₃ CClF₂ and CCl₂ FCCl₂ F can be reacted to obtain CClF₂ CCl═CClCClF₂ from CCl₃ CClF₂ and CClF═CClF from CCl₂ FCCl₂ F.

Homogeneously dispersed multiphase catalysts of ruthenium and fluorides of at least one element selected from the group consisting of Al, Co, Cr, Fe, V, Sc and Ga may be used in accordance with this invention in a process for increasing the fluorine content of compounds having the formula C_(j) H_(g) Cl_(h) F_(i), by reacting the compounds with HF in the vapor phase in the presence of the homogeneously dispersed multiphase catalysts. Suitable catalysts for this reaction include compositions consisting essentially of fluorides of at least one element selected from the above disclosed group homogeneously dispersed with ruthenium. Preferred catalysts are homogeneously dispersed ruthenium with CrF₃ or with beta-AIF₃.

The reaction of said compounds of the formula C_(j) H_(g) Cl_(h) F_(i) with HF in the presence of the catalysts of the instant invention is typically conducted at a temperature from about 150° C. to 400° C., preferably from about 150° C. to 375° C., and more preferably from about 175° C. to about 350° C. Typically the contact time is from about 1 to about 120 seconds, preferably from about 5 to about 60 seconds. The amount of HF ordinarily should be at least a stoichiometric amount. Typically, the molar ratio of HF to said compounds of the formula C_(j) H_(g) Cl_(h) F_(i) ranges from about 1:1 to about 20:1, preferably from about 2:1 to 10: 1, and more preferably from about 3:1 to 6:1. In general, with a given catalyst composition, the higher the temperature and the longer the contact time, the greater is the conversion to fluorinated products. The above variables can be balanced, one against the other, so that the formation of higher fluorine substituted products is maximized.

Examples of saturated compounds which may be reacted with HF include CH₂ Cl₂ and CCl₃ CF₃. Of note is a catalytic process for producing difluoromethane (i.e., HFC-32 or CH₂ F₂) by the fluorination of CH₂ Cl₂. HFC-32 is produced by reacting CH₂ Cl₂ with HF in the vapor phase in the presence of the catalysts of this invention. The reaction of CH₂ Cl₂ with HF in the presence of the catalysts of the instant invention is preferably conducted at about 150° C. to 350° C., more preferably about 175° C. to 250° C. Oxygen may be added, if desired.

Also of note is a catalytic process for producing 2,2-dichloro-1,1,1,2-tetrafluoroethane (CCl₂ FCF₃, i.e., CFC-114a) by the fluorination of CCl₃ CF₃.

Homogeneously dispersed multiphase catalysts of ruthenium and fluorides of at least one element selected from the group consisting of Al, Co, Cr, Fe, V, Sc and Ga may be used in accordance with this invention in a process for hydrodechlorinating compounds having the formula C_(k) H_(p) Cl_(q) F_(t), by contacting the saturated compounds with the homogeneously dispersed multiphase catalysts in the presence of hydrogen in the vapor phase. Suitable catalysts for this reaction include compositions consisting essentially of fluorides of at least one element selected from the above disclosed group homogeneously dispersed with ruthenium.

The reaction of said compounds of the formula C_(k) H_(p) Cl_(q) F_(t) with hydrogen is conducted in the presence of the catalysts of the instant invention. The reaction is typically conducted at a temperature from about 100° C. to 350° C., preferably from about 125° C. to 300° C., and more preferably from about 150° C. to about 250° C. Typically the contact time is from about 1 to about 100 seconds, preferably about 5 to about 60 seconds. Typically, the molar ratio of hydrogen to the said compounds of the formula C_(k) H_(p) Cl_(q) F_(t) can range from about 1:1 to about 10:1, preferably about 1:1 to 5: 1, and more preferably about 1:1 to 4:1.

Examples of saturated compounds which may be reacted with hydrogen include CCl₂ FCF₃ and CHCl₂ CF₃. Of note is a catalytic process for producing 2-chloro-1,1,1,2-tetrafluoroethane (i.e., CHClFCF₃ or HCFC-124) by the hydrogenolysis of CCl₂ FCF₃. HCFC-124 is produced by reacting CCl₂ FCF₃ with hydrogen in the vapor phase in the presence of the catalysts of this invention. The reaction of CCl₂ FCF₃ with hydrogen in the presence of the catalysts of the instant invention is preferably conducted at about 125° C. to 300° C., more preferably about 150° C. to 250° C.

Also of note is a catalytic process for producing 2-chloro-1,1,1-trifluoroethane (i.e., CH₂ ClCF₃ or HCFC-133a) and 1,1,1-trifluoroethane (i.e., CH₃ CF₃ or HFC-143a) by reacting CHCl₂ CF₃ with hydrogen in the vapor phase in the presence of the catalysts of this invention. The reaction of CHCl₂ CF₃ with hydrogen in the presence of the catalysts of the instant invention is preferably conducted at about 125° C. to 300° C., more preferably about 150° C. to 250° C.

The processes for dimerizing, dehalogenating, dehydrohalogenating, hydrofluorinating and hydrodehalogenating halogenated hydrocarbons in accordance with this invention may be conducted in any suitable reactor, including fixed and fluidized bed reactors. The reaction vessel should be constructed from materials which are resistant to the corrosive effects of hydrogen fluoride and hydrogen chloride such as Inconel™ nickel alloy and Hastelloy™ nickel alloy.

Atmospheric and superatmospheric pressures are the most convenient and are therefore preferred. The reaction products may be separated by conventional techniques such as distillation. It is noted that many halogenated hydrocarbon products of the above reactions form azeotropes with HF, HCl, or other halogenated hydrocarbons.

Without further elaboration, it is believed that one skilled in the art can, using the description herein, utilize the present invention to its fullest extent. The following preferred specific embodiments are, therefore, to be construed as merely illustrative, and does not constrain the remainder of the disclosure in any way whatsoever.

EXAMPLES 1-6C

Examples 1-6c were carried out using essentially the same procedure.

To make a composition having the formula (NH₃)₆ RuMF₆, stoichiometric quantities of (NH₃)₆ RuCl₃ and the M metal trichlorides (or an oxide when M═Ga, V) were weighed separately into a Teflon® (polytetrafluoroethylene) beaker. The specific quantities used in the examples are shown in Table I. The (NH₃)₆ RuCl₃ was dissolved in 20 mL of deionized water and 20 mL of 48 % aqueous HF (Solution A). The M metal trichlorides were dissolved separately in 10 mL of deionized water (Solution B). For the preparation of (NH₃)₆ RuVF₆ and (NH₃)₆ RuGaF₆ phases, V₂ O₃ and Ga₂ O₃ were used as starting materials and were dissolved in a mixture containing 5 mL of deionized H₂ O and 5 mL of 48% aqueous HF (Solution B). Solution B was added to solution A under constant stirring conditions. The precipitate which formed was filtered and washed with deionized water and dried at about 110° C. for about 12 hours.

                  TABLE I                                                          ______________________________________                                         Example  Compound    M cation source                                                                            (NH.sub.3).sub.6 RuCl.sub.3                   ______________________________________                                         1        (NH.sub.3).sub.6 RuAlF.sub.6                                                               AlCl.sub.3.6H.sub.2 O                                                                      3.0960 g                                          2.4150 g                                                                     2 (NH.sub.3).sub.6 RuScF.sub.6 ScCl.sub.3.6H.sub.2 O 3.0960 g                    2.5942 g                                                                     3 (NH.sub.3).sub.6 RuVF.sub.6 V.sub.2 O.sub.3 1.5480 g                           0.3748 g                                                                     4 (NH.sub.3).sub.6 RuCrF.sub.6 CrCl.sub.3.6H.sub.2 O 3.0960                      2.6645 g                                                                     5 (NH.sub.3).sub.6 RuGaF.sub.6 Ga.sub.2 O.sub.3 0.7740 g                         0.2343 g                                                                     6 (NH.sub.3).sub.6 RuFeF.sub.6 FeCl.sub.3 3.0960 g                               1.6230 g                                                                   ______________________________________                                    

(NH₃)₆ Ru_(1-x) Co_(x) AlF₆ compositions were prepared in a similar manner as that used for (NH₃)₆ RuMF₆ compositions. The compositions that were prepared are shown in Table IA.

                  TABLE 1A                                                         ______________________________________                                         Ex-                                                                              am-                                                                            ple Compound (NH.sub.3).sub.6 RuCl.sub.3 (NH.sub.3).sub.6 CoCl.sub.3                                              AlCl.sub.3.6H.sub.2 O                     ______________________________________                                         6a   (NH.sub.3).sub.6 Ru.sub.0.2 Co.sub.0.8 AlF.sub.6                                             2.4770 g  2.4143 g                                                                               0.5350 g                                    6b (NH.sub.3).sub.6 Ru.sub.0.5 Co.sub.0.5 AlF.sub.6 1.5481 g 2.4143 g                                             2.1398 g                                    6c (NH.sub.3).sub.6 Ru.sub.0.8 Co.sub.0.2 AlF.sub.6 0.6192 g 2.4143 g                                             1.3374 g                                  ______________________________________                                    

Powder X-ray diffraction patterns of the phases showed the formation of single phase products and could be indexed on the basis of a cubic unit cell (space group: Pa3). The lattice parameters, determined by indexing the observed x-ray diffraction data, are given in Table II. Infrared and Raman spectra of the phases showed the presence of hexaammine groups and the microprobe analysis of four of the representative phases showed the Ru:M:F ratio to be 1:1:6.

                  TABLE II                                                         ______________________________________                                                                  Lattice parameter a,                                    Example Composition ±0.001 Å (±.0001 nm)                           ______________________________________                                         1        (NH.sub.3).sub.6 RuAlF.sub.6                                                                    9.987 (.9987)                                          2 (NH.sub.3).sub.6 RuScF.sub.6 10.239 (1.0239)                                 3 (NH.sub.3).sub.6 RuVF.sub.6 10.125 (1.0125)                                  4 (NH.sub.3).sub.6 RuCrF.sub.6 10.090 (1.0090)                                 5 (NH.sub.3).sub.6 RuGaF.sub.6 10.096 (1.0096)                                 6 (NH.sub.3).sub.6 RuFeF.sub.6 10.128 (1.0128)                                  6a (NH.sub.3).sub.6 Ru.sub.0.8 Co.sub.0.2 AlF.sub.6  9.962 (0.9962)                                    6b (NH.sub.3).sub.6 Ru.sub.0.5 Co.sub.0.5                                    AlF.sub.6  9.940 (0.9940)                                6c (NH.sub.3).sub.6 Ru.sub.0.2 Co.sub.0.8 AlF.sub.6  9.900 (0.9900)         ______________________________________                                    

Thermogravimetric analysis of each of the product, between room temperature and 600° C., in nitrogen, showed the compounds to undergo decomposition between about 300° C. and 400° C., the weight loss corresponding to the formation of Ru metal and metal tri- or di-fluorides.

The compositions (Examples 1-6) were heated to about 300° C. to 400° C. for 3 hours in nitrogen and the X-ray of the resulting product showed the presence of essentially metallic ruthenium and metal fluorides (such as β-AlF₃). The results are given in Table III. The products were granulated to form 1.2 to 1.7 mm particles for catalyst evaluation.

                  TABLE III                                                        ______________________________________                                         Decomposition Products of (NH.sub.3).sub.6 RuMF.sub.6                              Example  Precursor     Product Catalyst                                    ______________________________________                                         1        (NH.sub.3).sub.6 RuAlF.sub.6                                                                 Ru + β-AlF.sub.3                                     2 (NH.sub.3).sub.6 RuScF.sub.6 Ru + ScF.sub.3                                  3 (NH.sub.3).sub.6 RuVF.sub.6 Ru + amorphous fluoride of                         vanadium                                                                     4 (NH.sub.3).sub.6 RuCrF.sub.6 Ru + CrF.sub.3                                  5 (NH.sub.3).sub.6 RuGaF.sub.6 Ru + γ-GaF.sub.3                          6 (NH.sub.3).sub.6 RuFeF.sub.6 Ru + FeF.sub.2                                ______________________________________                                    

General Procedure for Examples 7-24

For most of the experiments, the granulated catalyst was placed in a 5/8" (1.58 cm) Inconel™ nickel alloy reactor heated in a fluidized sand bath. It was heated to about 200° C. in a flow of nitrogen (50 cc/min) for about two hours. After this period, it was heated in a stream of hydrogen (50 cc/min) for about 2 hours at 200° C. prior to evaluation. Liquid feeds were delivered using a metering pump and were vaporized and mixed with either HF or hydrogen prior to entering the reactor. Vapor feeds were delivered using standard mass flow meters.

In some instances, a microreactor was used. It was made of 1/4" (0.64 cm) tubing of Hastelloy™ nickel alloy. The catalyst was charged into this reactor to a height of about 5.7 cm. Except where otherwise indicated, the amount of catalyst was 1.24 g in the case of Ru/β-AlF₃, 0.82 g in the case of Ru/CrF₃ and 0.70 g in the case of amorphous fluoride of vanadium. They were supported in the bottom by an Incone™ nickel alloy screen. Drying and reduction of these catalysts were done in the larger reactor above and the treated catalysts transferred to the microreactor for evaluation. Substrates to be evaluated were loaded into a Fisher-Porter® pressure tube maintained at about 25° C. Hydrogen was bubbled through the organic substrate to provide a vapor stream of the organic and hydrogen which was sent through the catalyst bed maintained at the desired temperature.

General Procedure for Product Analysis

The following general procedure is illustrative of the method used for both reactors. Part of the total reactor effluent was sampled on-line for organic product analysis using a Hewlett Packard HP 5880 or 5890 gas chromatograph equipped with a 20' (6.1 m) long×1/8" (0.32 cm) diameter tubing containing Krytox™ perfluorinated polyether on an inert carbon support. The helium flow was 35 mL/min. Gas chromatographic conditions were 70° C. for an initial hold period of three minutes followed by temperature programming to 180° C. at a rate of 6° C./minute. Unless indicated, the reported results are in mole %. Positive product identification was obtained using mass and infrared spectroscopy.

The bulk of the reactor effluent containing organic products and also inorganic acids such as HCl and HF was treated with aqueous caustic to neutralize the acids prior to disposal.

    ______________________________________                                         Legend                                                                         ______________________________________                                         F12 is CF.sub.2 Cl.sub.2                                                                           F13 is CClF.sub.3                                            F21 is CHCl.sub.2 F F22 is CHClF.sub.2                                         F31 is CH.sub.2 ClF F32 is CH.sub.2 F.sub.2                                    F112a is CCl.sub.3 CClF.sub.2 F113 is CCl.sub.2 FCClF.sub.2                    F113a is CCl.sub.3 CF.sub.3 F123 is CHCl.sub.2 CF.sub.3                        F123a is CHClFCClF.sub.2 F133a is CH.sub.2 ClCF.sub.3                          F114 is CClF.sub.2 CClF.sub.2 F114a is CCl.sub.2 FCF.sub.3                     F124 is CHClFCF.sub.3 F124a is CHF.sub.2 CClF.sub.2                            F134 is CHF.sub.2 CHF.sub.2 F134a is CH.sub.2 FCF.sub.3                        F143a is CH.sub.3 CF.sub.3 F152a is CH.sub.3 CHF.sub.2                         F215aa is CClF.sub.2 CCl.sub.2 CF.sub.3 F215ba is CClF.sub.2 CClFCClF.su                         b.2                                                          F215ca is CCl.sub.2 FCF.sub.2 ClF.sub.2 F215cb is CCl.sub.3 CF.sub.2                             CF.sub.3                                                     F225ca is CHCl.sub.2 CF.sub.2 CF.sub.3 F225cb is CHClFCF.sub.2 CClF.sub.                         2                                                            F225da is CClF.sub.2 CHClCF.sub.3 F216aa is CF.sub.3 CCl.sub.2 CF.sub.3        F216a is CClF.sub.2 CClFCF.sub.3 F216cb is CCl.sub.2 FCF.sub.2 CF.sub.3        F226da is CF.sub.3 CHClCF.sub.3 F236fa is CF.sub.3 CH.sub.2 CF.sub.3                              F356mff is CF.sub.3 CH.sub.2 CH.sub.2 CF.sub.3 HFA                            is CF.sub.3 COCF.sub.3                                       PCE is CCl.sub.2 ═CCl.sub.2 F1112a is CF.sub.2 ═CCl.sub.2                                 F1113 is CClF═CF.sub.2 F1114 is CF.sub.2                                  ═CF.sub.2                                                F1214ya is CCl.sub.2 ═CFCF.sub.3 F1215xc is CF.sub.2 ═CClCF.sub.                         3                                                            F1215yb is CClF═CFCF.sub.3 F1225zc is CF.sub.3 CH═CF.sub.2           F1316mxx is CF.sub.3 CCl═CClCF.sub.3 (cis/trans isomers)                     F1326mxz is CF.sub.3 CH═CClCF.sub.3 (cis/trans isomers)                    F1336mzz is CF.sub.3 CH═CHCF.sub.3 (cis/trans isomers)                     F151-10mcxx is C.sub.2 F.sub.5 CCl═CClC.sub.2 F.sub.5 (cis/trans         isomers)                                                                         F153-10mczz is is C.sub.2 F.sub.5 CH═CHC.sub.2 F.sub.5 (cis/trans        isomers)                                                                         F151-12mmtt is (CF.sub.3).sub.2 C═C(CF.sub.3).sub.2                      ______________________________________                                    

EXAMPLE 7 CCl₃ CF₃ →CF₃ CCl═CClCF₃ +CHCl₂ CF₃ +CH₃ CF₃ Ru/β-AlF₃ Catalyst (9.7 g, 10 cc)

The reaction of F113a and hydrogen was studied. The contact time for all runs was 20 seconds, except for the run at 206° C. which was 10 seconds. The molar ratios of H₂ :F113a were as shown in the table. Results in area % are shown below. The major product for the reaction was the dimer olefin.

    __________________________________________________________________________     Temp. ° C.                                                                    H.sub.2 : F113a                                                                     F143a                                                                              F356mff                                                                             F123                                                                              F113a                                                                              t-F1316mxx                                                                           c-F1316mxx                                                                           Others.sup.(a)                          __________________________________________________________________________     205   4    15.8                                                                               1.2  10.3                                                                              0.0 44.5  22.0  6.2                                       206 8 21.3 1.8 8.8 0.0 41.7 20.0 6.4                                           176 2 10.0 0.4 14.1 1.7 48.4 23.0 2.3                                          175 2 10.3 0.5 14.4 1.7 48.1 22.7 2.3                                          175 4 15.9 3.7 15.7 0.1 41.8 19.0 3.8                                          175 1 3.3 0.0 9.0 18.3 45.8 22.1 1.5                                         __________________________________________________________________________      .sup.(a) Others include CH.sub.4, C.sub.2 H.sub.6, F133a, F1336mzz, F114a      F1326mxz, F113, as well as unidentified products                         

EXAMPLE 8 CF₃ CCl₂ CF₃ →(CF₃)₂ C═C(CF₃)₂ +CF₃ CHClCF₃ +CF₃ CHClCF₃ Ru/β-AlF₃ Catalyst

Using the catalyst of Example 7, the reaction of F216aa and hydrogen was studied. The contact time was 20 seconds in all instances and results are reported in area %.

    __________________________________________________________________________     Temp. ° C.                                                                    H.sub.2 : F216aa                                                                     F1225zc                                                                             F236fa                                                                             F1215xc                                                                             F226da                                                                             F216aa                                                                             F151-12mmtt                                                                           Others.sup.(b)                        __________________________________________________________________________     175   1.0   0.6  4.9 7.5  29.6                                                                               46.8                                                                               7.9    2.7                                     200 1.0 1.6 8.6 8.1 38.5 22.7 16.9 3.5                                         200 0.5 0.3 3.9 4.5 17.1 57.4 14.1 2.5                                         250 0.5 0.2 2.7 2.4 10.0 54.8 28.4 1.7                                         300 0.5 0.0 1.1 1.8 13.4 54.0 27.8 1.9                                       __________________________________________________________________________      .sup.(b) Others include F216ba and F15310mczz, and small amounts of other      unknowns                                                                 

EXAMPLE 9 CHCl₂ CF₃ →CH₂ ClCF₃ +CH₃ CF₃ Ru/β-AlF₃ Catalyst

Using the catalyst of Example 7, the reaction of hydrogen and F123 was studied. The hydrogen-to-organic ratio was 1/1, the contact time 20 seconds and the reaction temperature 200° C. Results in area % are shown below. The products primarily correspond to those arising from the replacement of chlorine by hydrogen.

    ______________________________________                                         CH.sub.4                                                                             C.sub.2 H.sub.6                                                                       F143a    F133a F1336mzz F123 Others                               ______________________________________                                         1.1   1.1    30.8     21.2  0.3      44.0 1.6                                    0.7 0.8 24.2 20.9 0.3 51.4 1.7                                               ______________________________________                                    

EXAMPLE 10 CCl₃ CF₂ CF₃ →C₂ F₅ CCl═CClC₂ F₅ Ru/β-AlF₃ Catalyst

Using the catalyst of Example 7, the reaction of F215cb and hydrogen was studied. The hydrogen-to-organic ratio was 1/1 and the contact time was 30 seconds. The results are reported in area %. The starting feed contained 3.3 % F215aa, 95.8% F215cb and small quantities of other products. The major product of the reaction was olefinic dimer.

    ______________________________________                                         Temp.                        F151-10                                                                               F151-10                                      ° C. F225ca F215aa F215cb mcxx mcxx Others                            ______________________________________                                         175    2.6     0.0     2.4   82.1   10.3  1.2                                    176 2.1 0.1 2.5 82.6 10.7 1.1                                                  150 1.8 0.5 3.5 83.8 9.5 0.6                                                 ______________________________________                                    

EXAMPLE 11 CClF₂ CCl₂ CF₃ +CClF₂ CClFCClF₂ +CCl₂ FCF₂ CClF₂ →CF₂ ═CClCF₃ +CClF=CFCF₃ Ru/β-AlF₃ Catalyst

Using the catalyst of Example 7, the reaction of a mixture of F215 and hydrogen was studied. The contact time was 20 seconds in all cases. The molar ratios of H₂ :F215 mixtures were 1:1 except for the second 175° C. run where it was 2:1. The feed to the reactor analyzed for 25.5% F215aa, 63% F215ba and 11.4% F215ca in addition to small amounts of other products. The results reported are in area %. The primary products of the reaction are the uncoupled olefins.

    __________________________________________________________________________     Temp.          F225                                                              ° C. F1215xc F1215yb cb + ca F215aa F215ba F215ca Others              __________________________________________________________________________     150 40.8  5.6  0.4  0.4 40.2                                                                               9.5 2.9                                              175 46.4 8.1 0.5 0.1 32.6 9.3 3.0                                              175 49.4 9.6 0.7 0.0 27.5 9.1 3.7                                              200 50.3 10.1 1.0 0.0 26.4 8.7 3.5                                             250 58.2 15.1 7.3 0.0 12.2 1.5 5.7                                             275 59.9 16.6 8.1 0.0 8.8 0.6 6.0                                            __________________________________________________________________________

EXAMPLE 12 CCl₃ CF₃ →CF₃ CCl═CClCF₃ +CHCl₂ CF₃ Ru/β-AlF₃ Catalyst

Using the catalyst of Example 7, the reaction of hydrogen and HF with F113a was studied. The molar ratio of HF:H₂ :F113a was 2:1:1 for the 15 second contact time (C.T.) runs and was 2:0:1 for the 30 second contact time runs. The reaction temperature was 275° C. and the results reported below are in area %.

    ______________________________________                                         C.T.                            t-F1316                                                                              c-F1316                                    Sec. F143a F114a F123 F113a mxx mxx Others                                                                               .sup.(c)                           ______________________________________                                         15   1.5     1.1     16.1 2.5   46.9  28.1  3.8                                  15 0.8 0.9 9.6 15.3 44.1 26.4 2.9                                              30 0.0 1.3 0.2 96.6 0.7 0.5 0.8                                                30 0.0 1.5 0.0 97.2 0.4 0.3 0.6                                              ______________________________________                                          .sup.(c) Others include F113, F133a, PCE, F1326mxz, and minor quantities       of other unknowns                                                        

EXAMPLE 13 CCl₃ CF₂ CF₃ →C₂ F₅ CCl═CClC₂ F₅ Ru/β-AlF₃ Catalyst/Microreactor

Hydrogen (10 sccm, i.e., 1.67×10⁻⁷ m³ /s) was bubbled through liquid F215cb at about 25° C. and the gas mixture sent through the catalyst at 200° C. The major product observed was CF₃ -CF₂ -CCl═CCl-CF₂ -CF₃ (C₆ F₁₀ Cl₂, F151-10 mcxx, 75%). The cis and trans isomers of this compound were present in about a 10:65 ratio. The results are reported in area %.

EXAMPLE 14 CClF₂ CHClCF₃ →CF₃ CH═CF₂ Ru/β-AlF₃ Catalyst/Microreactor

Example 13 was repeated except that the organic feed was F225da. Product analysis indicated about 20 area % F1225zc, and about 2% unknowns, the remaining being starting material.

EXAMPLE 15 CH₂ Cl₂ +HF→CH₂ ClF+CH₂ F₂ Ru/CrF₃ Catalyst (13.2 g, 14 mL)

The reactor was charged with the catalyst and dried in a stream of nitrogen at 200° C. for about 2 hours prior to use. The reactor was operated at 200° C. with an HF-to-organic ratio of 4/1 and a contact time of 15 seconds. Product analysis indicated the following.

    ______________________________________                                         F32    F22    F31      F21  CH.sub.2 Cl.sub.2                                                                      CHCl.sub.3                                                                           Others                               ______________________________________                                         24.5   0.8    15.8     1.5  56.0    1.4   0.0                                    26.7 0.3 15.1 0.4 57.2 0.4 0.0                                                 28.1 0.1 14.6 0.2 56.9 0.1 0.0                                                 29.8 0.1 14.6 0.1 55.3 0.1 0.0                                                 31.9 0.1 14.4 0.1 53.5 0.1 0.0                                               ______________________________________                                    

EXAMPLE 16 CCl₃ CF₃ +HF→CCl₂ FCF₃ Ru/CrF₃ Catalyst (13.2 g, 14 mL)

Using the catalyst of Example 13, the fluorination of F113a was carried out. The HF-to-F113a ratio was 2:1, and the contact time was 15 seconds. The following results were obtained.

    ______________________________________                                         Temp., ° C.                                                                         F13    F114a      F1112a                                                                               F113a                                      ______________________________________                                         250         0.1    14.8       0.2   84.8                                         275 0.1 31.3 0.6 67.9                                                          300 0.1 63.4 1.0 35.4                                                        ______________________________________                                    

EXAMPLE 17 CCl₃ CF₂ CF₃ →C₂ F₅ CCl═CClC₂ F₅ +CCl₂ ═CFCF₃ Ru/CrF₃ Catalyst/Microreactor

Example 13 was substantially repeated except that the catalyst was Ru/CrF₃. In addition to cis/trans F151-10mcxx (75 area %), about 22 area % 1214ya was also observed.

EXAMPLE 18 CClF₂ CHClCF₃ →CF₃ CH═CF₂ Ru/CrF₃ Catalyst/Microreactor

Example 14 was substantially repeated except that the catalyst was Ru/CrF₃. Area % product analysis indicated about 16% F1225zc, and about 2% unknowns, the remaining being starting material.

EXAMPLE 19 CClF₂ CClFCF₃ →CF₂ ═CFCF₃ Ru/β-AlF₃ (A) or Ru/CrF₃ (B) Catalyst/Microreactor

Hydrogen (10 sccm, i.e., 1.67×10⁻⁷ m³ /s) was bubbled through liquid F216ba maintained at about 25° C. The vapor mixture was passed through the catalysts maintained in independent microreactors. The major olefinic product was hexafluoropropylene (HFP, CF₃ CF═CF₂). Average product analysis from the two catalysts in area % is shown below.

    ______________________________________                                         Temp., ° C.                                                                     Catalyst HFP    F1215yb  F216ba                                                                               Unknowns                                ______________________________________                                         200     A        6.6    0.0      92.9  0.5                                       250 A 22.9 0.0 76.4 0.4                                                        300 A 41.9 0.0 55.3 2.8                                                        200 B 5.7 1.2 90.4 2.7                                                       ______________________________________                                    

EXAMPLE 20 CCl₂ FCClF₂ →CClF═CF₂ Ru/CrF₃ Catalyst/Microreactor

Hydrogen, 1.5 sccm (2.5×10⁻⁸ m³ /s), was bubbled through F113 maintained at about 25° C. and the mixture sent through the catalyst bed at 200° C. Area % product analysis indicated 13.3% chlorotrifluoroethylene (CTFE, CClF═CF₂), 5.5% F123a and 4% F123 in addition to unconverted starting material, and small quantities of other products.

EXAMPLE 21 CCl₃ CF₃ →CF₃ CCl═CClCF₃ +CHCl₂ CF₃ Ru/FeF₂ Catalyst (7.7 g, 5 mL)

The reactor was charged with Ru/FeF₂ dried in a stream of nitrogen and reduced in a stream of hydrogen according to the general procedure prior to use. The reactor was operated at 175 ° C. with a hydrogen:F113a ratio of 1:1 and at a contact time of 20 seconds. The results are reported in area %.

    ______________________________________                                                                      t-F1316                                                                               c-F1316                                      F143a F114a F123 F113a mxx mxx Others                                        ______________________________________                                         1.3    0.6     15.3    5.6   50.2   25.7  1.3                                    1.0 0.6 13.2 9.0 49.6 25.7 1.0                                                 0.9 0.6 12.3 10.7 49.1 25.6 0.9                                              ______________________________________                                    

EXAMPLE 22 CCl₂ FCF₃ →CHClFCF₃ Ru/FeF₂ Catalyst (7.7 g, 5 mL)

Using the catalyst of Example 19, the reaction of hydrogen and F114a was carried out. The hydrogen-to-organic ratio was 2:1 and the contact time 20 seconds.

    __________________________________________________________________________     Temp., ° C.                                                                   CH.sub.4                                                                          C.sub.2 H.sub.6                                                                   F143a                                                                              F134a                                                                              F124                                                                              F133a                                                                              F114a                                                                              F123                                                                              Others                                       __________________________________________________________________________     175   0.4                                                                               0.4                                                                               1.0 0.1 10.1                                                                              0.6 85.6                                                                               1.2                                                                               0.7                                            200 1.4 0.8 1.5 0.2 24.1 0.5 70.2 0.6 0.7                                      225 3.7 1.4 2.8 0.6 41.4 0.7 47.6 0.5 1.3                                    __________________________________________________________________________

EXAMPLE 23 CF₃ CCl₂ CF₃ →(CF₃)₂ C═C(CF₃)₂ +CF₂ ═CClCF₃ +CF₃ CHClCF₃ Ru/FeF₂ Catalyst (7.7 g, 5 mL)

Using the catalyst of Example 19, the reaction of hydrogen and F216aa was carried out at a contact time of 20 seconds. The reported results are in area %.

    __________________________________________________________________________     Temp. ° C.                                                                    H.sub.2 : 216aa                                                                     F1215xc                                                                             F226da                                                                             F216aa                                                                             C.sub.6 F.sub.10                                                                  C.sub.6 HF.sub.11                                                                  F151-12mmtt                                                                           Others                                   __________________________________________________________________________     200   2.0  38.2 21.8                                                                               20.8                                                                               1.1                                                                               1.0 15.1   2.0                                        200 1.0 25.7 14.4 39.8 1.0 1.0 16.4 1.6                                        200 0.5 16.3 8.4 58.1 0.8 0.7 14.3 1.4                                         250 0.5 19.9 7.7 52.0 0.5 0.3 18.1 1.6                                         300 0.5 15.2 12.9 55.6 0.3 0.2 13.8 2.2                                      __________________________________________________________________________

Compounds of the formulas C₆ F₁₀ and C₆ F₁₁ H were determined by mass spectrometry.

EXAMPLE 24 CClF₂ CClFCF₃ →CF₂ =CFCF₃ Ru/Amorphous Vanadium Fluoride Catalyst/Microreactor

Example 17 was substantially repeated at 200° C., except that ruthenium/amorphous vanadium fluoride catalyst was used. Area % product analysis indicated 36.7% HFP and 58.5% starting material, the remaining being unknowns.

EXAMPLE 25 CClF₂ FCClF₂ +CCl₃ CF₃ →CF₃ CCl═CClCF₃ +CHCl₂ CF₃ +CH₃ CF₃ Ru/β-AlF₃ Catalyst/Microreactor

Through the microreactor, maintained at 150° C. and containing 0.54 g catalyst, was passed a vapor stream containing 90.3% F113 and 8.8% F113a and hydrogen, obtained by bubbling hydrogen through the liquid mixture maintained at 25° C. The total organic and hydrogen feed rate to the reactor was 10 cc/min. Product analysis in area % indicated 1.4% F143a, 2.6% CTFE, 2.3% F123, 85.8% F113, 4.5% of a cis/trans mixture of F1316mxx and small quantities of other products. 

What is claimed is:
 1. A process for decreasing the chlorine to carbon ratio for halogenated hydrocarbons containing chlorine and from 1 to 6 carbon atoms, in the presence of a multiphase catalyst, characterized by:(1) preparing a single phase solid catalyst precursor which has a structure that collapses at a temperature of about 400° C. or less and has the formula (NH₃)₆ Ru_(l-r-s) Co_(r) Cr_(s) MF₆, where r+s is in the range of 0.00 to 0.99, and M is at least one trivalent metal selected from the group consisting of Al, Cr, Fe, V, Sc and Ga; and (2) producing said multiphase catalyst by heating said single phase solid catalyst precursor to about 400° C. or less in a non-oxidizing atmosphere to produce a multiphase composition wherein a phase containing ruthenium is homogeneously dispersed with a phase containing metal fluoride.
 2. The process of claim 1 wherein two chlorine substituents are removed from a compound having the formula C_(n) H_(a) Cl_(b) F_(c) where n is an integer from 1 to 4, a is an integer from 0 to 1, b is an integer from 2 to 9, c is an integer from 0 to 9, where a+b+c equals 2n+2, and where two chlorines that are removed are on the same carbon atom, and the compound is dimerized by reacting said compound with hydrogen in the vapor phase to produce an olefin of the formula C_(2n) H_(2a) Cl_(2b-4) F_(2c).
 3. The process of claim 1 wherein a saturated compound having the formula C_(m) H_(d) Cl_(e) F_(f) where m is an integer from 2 to 6, d is an integer from 0 to 2, e is an integer from 2 to 4, f is an integer from 3 to 12, where d+e +f equals 2m+2, is dehalogenated by reacting said compound with hydrogen in the vapor phase to produce an olefin of the formula C_(m) H_(d) Cl_(e-y) F_(f-y), where y is an integer from 1 to 2 when m is an integer from 2 to 3, and y is an integer from 2 to 4 when m is an integer from 4 to 6, provided that a chlorine atom on each of two adjacent carbons or a fluorine and a chlorine atom on two adjacent carbons, but not a fluorine atom on each of two adjacent carbons are removed.
 4. The process of claim 3 wherein CClF₂ CHClCF₃ is reacted with hydrogen to produce CF₂ ═CHCF₃.
 5. The process of claim 3 wherein CF₃ CFClCF₂ Cl is reacted with hydrogen to produce CF₃ CF=CF₂.
 6. The process of claim 1 wherein the fluorine content of either a saturated compound or an unsaturated olefinic compound having the formula C_(j) H_(g) Cl_(h) F_(i) where j is an integer from 1 to 6, g is an integer from 0 to 4, h is an integer from 1 to 13, i is an integer from 0 to 13, provided that h is at least 1 when the compound is saturated, is increased by reacting said compound with HF in the vapor phase.
 7. The process of claim 1 wherein a cyclic or acyclic compounds having the formula C_(k) H_(p) Cl_(q) F_(t) where k is an integer from 1 to 6, p is an integer from 0 to 12, q and t are integers from 1 to 13, where p+q+t equals 2k+2, when the compound is saturated and acyclic, equals 2k when the compound is saturated and cyclic or is olefinic and acyclic, and equals 2k-2 when the compound is olefinic and cyclic, is hydrodehalogenated by reacting said compound with hydrogen in the vapor phase.
 8. A single phase fluoride composition of the formula (NH₃)₆ Ru_(l-r-s) Co_(r) Cr_(s) MF₆, where r+s is in the range of 0.00 to 0.99, and M is at least one trivalent element selected from the group consisting of Al, Cr, Fe, V, Sc and Ga.
 9. A multiphase catalyst composition consisting essentially of metallic ruthenium and fluorides of at least one element selected from the group consisting of Al, Co, Cr, Fe, V, Sc and Ga, wherein said ruthenium is homogeneously dispersed with phases of said fluorides.
 10. The multiple catalyst composition of claim 9 produced by the process of (1) preparing a single phase solid catalyst precursor which has a structure that collapses at a temperature of about 400° C. or less and has the formula (NH₃)₆ Ru_(l-r-s) Co_(r) Cr_(s) MF₆, where r+s is in the range of 0.00 to 0.99, and M is at least one trivalent element selected from the group consisting of Al, Cr, Fe, V, Sc and Ga, and (2) producing said multiphase catalyst by heating said single phase solid catalyst precursor to about 400° C. or less in an non-oxidizing atomsphere to produce a multiphase composition wherein a phase containing ruthenium is homogeneously dispersed with a phase containing metal fluoride.
 11. A single phase fluoride composition of claim 8 having the formula (NH₃)₆ RuAlF₆.
 12. A single phase fluoride composition of claim 8 having the formula (NH₃)₆ RuScF₆.
 13. A single phase fluoride composition of claim 8 having the formula (NH₃)₆ RuVF₆.
 14. A single phase fluoride composition of claim 8 having the formula (NH₃)₆ RuCrF₆.
 15. A single phase fluoride composition of claim 8 having the formula (NH₃)₆ RuGaF₆.
 16. A single phase fluoride composition of claim 8 having the formula (NH₃)₆ RuFeF₆.
 17. A single phase fluoride composition of claim 8 having the formula (NH₃)₆ Ru₀.8 Co₀.2 AlF₆.
 18. A single phase fluoride composition of claim 8 having the formula (NH₃)₆ Ru₀.5 Co₀.5 AlF₆.
 19. A multiphase catalyst composition of claim 9 consisting essentially of metallic ruthenium and fluorides of Al.
 20. A multiphase catalyst composition of claim 9 consisting essentially of metallic ruthenium and fluorides of Cr. 